Product of reaction of phosphorus sulfide, and hydrocarbon, with guanidine carbonate



:detergent additive.

The art of metallic detergents for! lubricating oil compositions adapted for use in internal combustionrengines is well known to those versed in Patented Oct. 7, 1952 PRODUCT OF REACTION OF PHOSPHORUS "SULFIDE, AND "'HYDROCARBON, WITH GUANIDINE'CARBONATE V Max Hilh Sornerville, N. J., assignor to Standa ard Oil Development Company, a corporation of Delaware N Drawing. Application April 23, 1949,

Serial No. 89,370

- r This inventionrelates to. mineraloil compositions and particularly to lubricants containing, a

this field and has resulted in substantial improvements in lubricants. Thes detergents are particularly useful in lubricating oil compositions which are employedin internal combustion engines used in the operations of automobiles, aircraft and similar vehicles, including Diesel engines, to improve their operation by preventing or retardingcorrosion, piston ring sticking'cylinder wear, and carbonand varnish l formation.

However, when metallic detergents. are used in lubricating compositions where oil consumption is highand engine con-ditionsare severe, such as in aircraft engines or where such concentrations of metallic detergents areused to maintain engine cleanliness under :conditions Where high deposit -fuels ofcracked or high sulfur 'nature'are used,

such. as in automobile and Diesel operation, the

.ash content from the metallic detergent accumulates in the combustion chamberand causes pre-ignition, detonation, spark plug fouling, valve burning,v and ultimate destruction of the engine.

" 'It has been found, in accordance with the present invention, that if the reaction product ofa phosphorus sulfide-with an essentially-hydrocarbonproduct is neutralized with guanidine or any of.-its: derivatives as hereinafter defined or with any other compound containing a guanyl radical, the product so formed is very stable at .the temperatures of engine operation and serves the purpose of a good detergent and anti-oxidant.

'When incorporated in mineral lubricating oil which is 'used in an internal combustion engine,

and becauseit contains no metal, it is free from the objectionable feature cf;leaving a metallic deposit or ash. These compounds are effective .not only when added directly tothe crankcase lubricant but also, when added to the engine fuel, since in the operation of the engine it will work its'way from thecombustion chamberinto thecrankcase and there blend with the lubricant. Guanidine and guanidine derivatives may be employed as the basic reagents for neutralizing the titratable acidity of the phosphorussulfidehydrocarbon reaction product. The free base guanidine and its derivatives may be used as well asjbasic acting saltsof suchbases, by whichis meantsalts of acids whose strength, measured on a 1:11 scale, is less than that of theacidic phosphorus sulfide-hydrocarbon product. 3 Such reclaims. (or. 260-132) isooctyl, 2-ethylhexyl,. decyl, dodecyl, .tetradecyl, cetyl and stearylradicals. R, R and Rf may also represent cycloalkyl, ar ylalky1,'- aryl or alkylaryl illustrating the-'above' -describ d' types are the definedby the formula -s-Blisey i l fl ei ,s-Bten su e, j l ;qyclohexylguanidine b s c acting salts are, for example, the carbonates of guanidine and its derivatives. J Alternatively, the final products may be iormedby, double decomposition of a salt-of guanidineior' guanidine derivative, e. g., guanidine' hydrochloride or sulfate, With a metal salt of 'th'e phosphorus sulfide-hydrocarbon reaction product. "Although guanidine and its saltsar e preferred, substituted lguanidines may be used; Broadly, the guanidine type basic compounds' which maybe reacted in accordance witht he present invention may be in whichzR, landHR"; represent hydrogen or hydrocarbon groups. containing 1-:,to, 20 carbon atoms, e. ;g.,:: straight chain alkyl'groups, such as methyl, ethyljpropyl, butyl, alsoghigher: straight and branched chain alkyl' groups,: such. as octyl,

groups, for example, methylcyclohexyl, phenylethyl, phenyl, cresyl, and tert.i-butylphenyl groups; ,lt will be understoodthat R',R' and R .can bethe same or different atoms orgroups in the'same molecule..iHoweve1-,' in'the case'of a ,substituted guanidine it is most preferable to em- -ploy symmetrically tri substituted compounds,

and-alkyl and cycloalkyl groups-are the more preferred types of substituting groupa' These include the symmetrical trialkyl, trinap'hthenyl, and triarylalkyl guanidines. Also highly preferred' classes of substituted guanidines include the 'monoalkyl, mononaphthenyl; and monoaralkyl guanidines; unsymmetric'al' dialkyl, di-

naphthenyl, and dia'rylalkyl guanidinesf Somewhat less'preferab'le but still useful classesare the symmetrical-f dialkyl dinaphthenylf and dia'r'yl al yl g'uanidines, and the mono-, di ,'andtriaryl guanidines. I Still other substituted "guanidines and dicyandiamidine- Specific-examples ofbasic acting compounds may be used, such) as big-uanide," dicyafndiamide,

following? jeuamam i; I a-Methylguanidine -Ethylguanidine a-Hexylguanidin ,1. t ,euanidinev a-Decylguanidine a-Hexadecylguanidine a-Octadecylguanidine a-Phenylguam'dine a,a-Dimethylgua'nidine a,a-Diethylguanidine a,a-Diisoamylguanidine a,a-Dihexy1guanidine a,a-Diheptylguanidine a,a-Diphenylethylguanidine a,a-Dibenzylguanidine a,a-Dicyclohexylguanidine a,a-Didecylguanidine a,a-Dihexadecylguanidine a,a-Dioctadecylguanidine a,a-Diphenylguanidine The (av-substituted guanidines corresponding to the above-listed a a-substituted compounds.

"Carbonatesof any of the above listed compounds. The-sulfide of phosphorus-which is employed in the-reaction with hydrocarbon material may be P283, P255, P483, P481 orotherphosphorus sulfide, and is preferably phosphorus pentasulfide, P255.

The hydrocarbon material which may be re- "acted witha phosphorus sulfide in the'first step of the production. of additives-of the present invention. may-be parafilns, olefins .or olefin poly- .zmers', diolefins, acetylenes, aromatics or alkyl aromatics, cyclic .aliphatics, petroleum fractions, .such -as lubricating oil fractions, petrolatums, 'waxesmr'acked cyclestocks; or condensation prod- .ucts. of petroleum fractions, .solvent extracts of petroleum fractions; etc. wEssentially paraffinic hydrocarbons such as brightstock residuums,-lubricating oil distillates, .petrolatums or. parafiixrwaxes may be employed. There may also be employed. products obtained ycondensing any ofthe foregoinghydrocarbons, usual-lythrough firstihalogenating the hydrocarbon; with aromatichydrocarbons in the presence of anhydrous inorganichalides, such as aluminum-z chloride, zinc' chloride, boronfluoride-"and vthe like. Aseexamples of monoolefins may be mentioned isobutylene, acrolein, decene, dodecene, cetene (C octadecene (C13), cerotene (Czs),:melene (Cat), olefinie extracts: f-romgasoline or gasoline itself, cracked cycle stocks and polymers thereof, resin oils-from crude oil, hydrocarboncoalresins, rcr'acked waxes, .dehydrohalogenated chlorinated waxes, and any mixed high molecular weight alkenes obtained: by cracking petroleum oils. A preferred class of olefins are-those having at least -20 .carbon atoms per molecule, of-whichfrom about 12. to abouti18 carbon'atoms, andpreferably at least carbon atoms, are in a long chain. Such olefins may be obtained by the dehydrogenation of parafiin waxes, by the dehydrolialogenation of long chain alkylf ha-lidea' 'by 'the synthesis of hydrocarbons from' ;CO"and"H'2';"by the dehydration of alcohols, etc.

Another class of suitable olefinicmateriaflsare the monoolefin polymers, inwhich 'the'mqlecular weight ranges from 100 to 50,000; preferablyfrom and the-like.

be obtained by the polymerization of low molecular weight monoolefinic hydrocarbons, such as ethylene, propylene, butylene, isobutylene, normal and isoamylenes, or hexenes, or by the copolymer-ization of any combination of the above monoolefinic materials.

Diolefins which may be employed include well known materials such as butadiene, isoprene, chloroprene, eyclopentadiene, 2,3-dimethylbutadi'ene, 'pentadiene-LB, hexadiene-2,4, terpenes,

Acetylene and substituted acetylenes may similarly be employed.

- Another class'of unsaturated hydrocarbon materials whichmaybe advantageously employed in the preparation of the additives of this invention are high molecular weight copolymers of low P molecular weight monoolefins and diolefins. The

copolymer is prepared by controlled copolymerization of a low molecular weight olefin and a nonaromatic hydrocarbon showing the general formula' Ci H21L-a'l7, in which a: is 2 ora multiple of 2; in thepresence of a catalyst of the Friedel- Crafts or peroxide type. The low molecular weight olefin is preferably an isoolefin or'a tertiary base olefin preferably one having less than 7- carbon atoms per molecule. Examples of such olefins are isobutylene, Z-methylbutene-1,2-ethylbutene-l, secondary and tertiary base amylene, hexylenes, andzthe like. Examples of the non- :aromatic hydrocarbons of the above formula which can .be used are the conjugated diolefins listed in the preceding paragraph, diolefins such asrlA-hexadiene, in which the double bond is not conjugated,.as well as the acetylenes. The .copolymerization is preferably carried out in the presence of aluminum chloride, boron fluoride, or benzoyl peroxide, and the copolymer is preferably one having a molecular weight of about 1,000 to 30,000.

Another class of hydrocarbons which may be employed in a similar manner are aromatic hydrocarbons, such as benzene, naphthalene; anthracene', toluene, xylene, diphenyl, and the like, as well as aromatic hydrocarbons having alkyl .substituents, and aliphatic hydrocarbons having 'aryl substituents.

. Astill further class of hydrocarbons which maybe employed in the'reaction with sulfides ofphosphorus are condensation products of halogenated aliphatic hydrocarbons with an aromaticcompoun'd, produced by condensation. in the presence'of aluminum chloride or other Friedel-Crafts ty ecatalyst. The halogenated aliphatic hydrocarbon is preferably ahalogenated. long "chain paraffin. hydrocarbon having more-thanr8 carbon atoms, such as 'para'flin' wax, petrolatum, ozoceritewax, etc. High viscosity .parafiln .oils, particularly heavy residual: oil whichvhas been treated: with chemicals or extracted with'pro'pane or other solvents for :the removal .of asphalts may be employed. The

aromatic constituent may be naphthalene, fluorene, phenanthrene; anthracene, coal tar residues, and the like.

Another i type of hydrocarbon material which maymbe similarly employed is a resin-like oil wlii'cli has a molecular-'wei'ght'of from about 1,000 toll-000 or highenobtained preferably'from a paraflinlc oil-which has been dewaxed and which is-"then treated with a liquefied normallygaseous hydrocarbon, e. 'propane, to precipitate a heavy propane-insoluble fraction. The latter is asubstantially-wax-free"and asphalt-free prod- 1 ctliaVing-a Saybol't 'viscosity'at 210 F. of about about 250 to about 10,000. 'rhete 101mm:rs'-may 112000 to f i llll conds or'more.

as e -m 'Ihe additive employed in the present inven- ;tion is the neutralized-reaction productobtained .by reacting one or more of the hereindescribed hydrocarbons with a phosphorus sulfide, preferablyphosphorus pentasulfide. Theiphosphorus sulfide-hydrocarbon reaction product may be readily obtained by reacting the phosphorus sulfide with. the hydrocarbon at a temperature of about 200-E. to about 600 F., and preferably from about 300 F. to about 550 F., using from about 1 to about 10, preferably about 2 to about 5, molecular proportions of hydrocarbon to 1 molecular proportion of the sulfide of phosphorus in the reactions-It is advantageous'to maintain a non-oxidizing atmosphere, such as an atmosphere of nitrogen, above the reaction mixture. Usually it is desirable to usean amount of the phosphorus sulfide that will completely react with the hydrocarbonso thatno further purification becomes necessary. In the case or 1 employed in mineral lubricating oils, they are preferably added in proportions of about0001 to about 10.0% and preferably 1.0 to about 6.0%.

The proportions giving the best results will vary somewhat according to the nature of the additive and the specific purpose which the lubricant is to'serve in a given case. Forcommercialpur? poses, it is convenient to prepare concentrated oil solutions in which the amount of additive in the composition ranges from to 50% by weight, and to transport and store them in such form. In preparing a lubricating oil composition for use as a crankcase lubricant the additive concentrate is merely blended with the base oil in the required amount.

In certain cases it may be found that the eifect of adding compounds of the type described above to a lubricating oil will be to increase the detergent effect of the oil without sufficiently monoolefin polymers the preferred ratio is one molecular proportion of the sulfide of phosphorus to two, to five molecular proportions of polymer.

.Insuchcase thereaction is continued, until all ors'ubstantially all of the phosphorus sulfidehas reacted. Th reaction timeis not criticahand the time required to cause the maximum amount of phosphorus sulfide to react will vary greatly with thetemperature. A reaction time of 2 to l0:hours is frequently necessary. If desired, the reaction productmay be further treated by blowin with steam, alcohol, ammonia, or anamine at an elevated temperature of about 200 F. to about 600 F. to improve the odor thereof.

, The neutralized phosphorus sulfide-hydrocarbon reaction productmay then be prepared by reacting the above phosphorus sulfideehydrocarbon reaction product with the organic basic compound,such as guanidine or guanidine derivative of the type described above. This reaction may becarried out, preferablyin a non-oxidizing atmosphere, by contacting the phosphorus sulfide.- ihydrocarbonreaction product, eitheriassuch or d-issolved in asuitable solvent such as naphtha, with the basic compound, preferably at .a, temperature of about 100 F. to 400 It isdesirable to employ at least enough of the basic compound to neutralize the titratable acidity of the phosphorus sulfide-hydrocarbon product. In practice a somewhat greater amount of basic compound is generally employed, since the basic compound can be reacted in proportions greater than that required for the neutralization of the titratable acidity. When the basic compound is added inthe form of a carbonate, the completion --of the reaction is indicated by a cessation of car- ;bon dioxide evolution. Ithas been found that somewhat superior products are formed when a water-soluble basic compound, e. g.,. guanidine carbonate, is dissolved in or mixed with water when contacted, with the phosphorus sulfidehydrocarbon reaction product. In the case of guanidine carbonatejit is preferable to employ a mixture ofythe salt and water containing 130 70% by weight Of the salt.

Since they additives-of the present invention are to be dissolvedin mineral oils, the hydrocarbons which are reacted with a sulfide of phosphorus and the guanyl compounds will be chosen with a View to provide a product which is solublein the oil base or which has such marginal solubility that it can be plasticized with a high molecular weight alcohol, ester, or other plastif 'cizers. 1

When additives of the present invention are solution was filtered providing oxidation resisting characteristics. In such a case it is advantageous to add to the lubricant, in addition to the additives of the present invention, a substance -,containing sulfur and/or phosphorus. Elemental sulfur may-be used for this purpose or an :organic, sulfur com.- pound, particularly an organic,- sulfur compound capable of being, decomposed to give freesulfur at .a temperature to whichthe lubricant is subjected during use. Examples of such organic sulfur compounds are sulfurized mineral -oils,

terpenes, olefins, and diolefinssulfurized animal and vegetable oils, sulfurized isobutylenepolymer, etc. r Below are given detailed descriptions of preparations of examples of lubricating oil additives described above as Well as jengine tests in which an oil containing theadditives was used as the lubricant. It is to be understood that these examples are given as illustrations of the present invention and are not to be construed .as limiting thescopetherecf in anyway.

Eac-amp lef'i f I 202 grams (0.8 mol) of octadecene was dissolved in an equal weight of a conventional1yrefined Coastal distillate oil in a three-necked-round bottomed flask, equipped with a stirrer, solids addition flask, nitrogen inlet tube, and condenser. .The temperature of the. mixture was raisedto 125 C. and l grams (0.2 mol) of phosphorus ,pentasulfide was added over a period of, one hour.

, of silicone fluid was added to minimize foaming during this operation. After the guanidine carbonate was added the temperature was raised to 144 C. and then retained at this point for two hours, after which the solution was filtered.

Example 2 A guanidine product in the form of a concentrate was prepared in the manner and from the materials described in Example 1, except thatin the step of neutralization with guanidine carbonate 88 grams of the concentrate of PzSa-ootadecene product wastreated with a mixture-of 5 I 7 grams; ofguanidine carbonate-and lgram of water; I

A Example 3 Reactions were. .carried out. as in Example '2, ,exceptthat amixture of 5..grams of'guanidine carbonate. and? grams of.water was ,used in the neutralization reaction.

. ,.;.:Ezample *4 1200- grams of Y polyisobutylenecf a molecular Was-conductedby operating-the Lauson engine at 1800 B. P. for =20--hours with a' 1.5indicated -kilowatt-lo ad,-'300-" F. oiltemperature and-295'-F. jacket --temperature. A- similar test was applied 5 'to the unbl'ended base'oil. 'Ihe oils-were rated by the demerit system,- Whereina perfectly-clean surfaceisgiven a=rating of-O, while a rating-of is given tothe worst condition whichcould be expected of that surface.- The results are shown 10 inthe following table:

Concentration Hydrocarbon .oLGuauidinefl 7 Oil Composition ,Reacted with Garbonatein jvamish P185 aduetoiglsl Solu- {nemem -Base oil ..i3.'8 Base-oll+2.% product-.oiExample 1.... octadeccne... 0.8 Baseoll+2% product'oi Example 2.... Octadecene.;'. 83% 0.4 ..Base.oil+2% product ofIExample 3.--. vOctadecene... .1 0.0 Base.oil+2% productof Example 4.... Polyisohutene 0.8 Base oil+2% prod'uctot Example 5.... Polyethyi pe. 1.4 ,Base'oil+2% product cf.Example 6.-.. ,1 Polybutene-l... .1. 4

weight. of about 1200- was-placed in a three-liter, threemecked round bottom flask and heated to 300 F. 125 grams of phosphorus pentasulfide was added and the temperature raised to400 F. over :a: two-hour period,- and heating a was con- 'tinued at -th'is temperature for'threemore-hours with stirring. The mixture was blown'with nitro- .gen for another five hours at 400 F; andthen filtered. 200 grams of -the phosphorus pentasulfide-treated polyisobutylene thus prepared was dissolved in 200 g. of a solvent extracted Mid- Continent distillate oil of 150 seconds (Saybolt) at 1'00- F. and treated withg. of guanidine carbonate dissolved in g. of water at-130 C. 1 for three hours and filtered.

Ezvample 5 152.5 grams ofpolyethylene of molecular weight of about 400 was placed in a reaction flask-asin Example 4 and heated to300 F. 30 grams of phosphorus pentasulfide was added and the temperature raised to400 F. and held at this point for 6 /2 hours, after which the reaction mixture -Wasfiltered. 'The product was diluted with 150 "grams ofa solvent extracted Mid-Continent distillate oil of 150 seconds (Saybolt) viscosity at 100F. 200 grams of this solutionwastreated-at 1300" F. with 40 grams of guanidine carbonate dis- Example 7 The guanidine products prepared by the methods of Examples 1 to 6 were blended in a lubricating oil baseconsisting of a solvent extracted Coastal naphthenic oil of seconds viscosity (Sayboltiat 210 F. -1?he blends-contained 4 weight ai time-concentrates (2-wt. of-active ingredients); The blends -were submitted to a "standard twenty-hour Lauson engine-test; which l hese results show thetexcellent detergency characteristics of the guanidine productsand-also show'that the use of-aqueous-solutions of-guanidine carbonate givesan-improved product over theme of solid-guanidine carbonate. 'The mechanism by which the use of water :givesanimproved product is-notdefinitely known; However, it is apparently related to-the effect of-w-ater or steam in causing-a decrease in thesulfur content below the theoretical value.

-Eitample' 8 Ablend-containing z4r%.;by weight oj,the:5'0% concentrate of guanidine. product prepared asidescribedin Example .1 (2%.- ofxactive ingredient) 1 in a solvent extracted. paraflinic type: of mineral lubricating oil of SA'E:- 30zviscosity gradeanda :sample. of the unblende'di oil base were employed as the crankcase lubricant in 36 hourxiests' with a Chevroletengine operated. at 30' brake" horsepower, 3150 R. P. M. speed, 280 F. oil temperature and 200 F. jacket.- temperat-uret Thepistonv skirt Example!) 'A- blend containing 4% of a the product of '-Example -'1 (2% ofactive-ingredient)-in a'-solvent extractedparaifinictype mineral lubricating oil of-=-S AE- 30= viscosity grade anda sample of the -u-nblendedbase oil --were-employed as 'thecrankcase' lubricant in tests-with-a caterpillar' -diesel engine operatedfor =-12O hours: and S -hours of :brea'k-in time'for'each-test, at approximately 19.8

brake horsepowery 1000 R.."P. -M-.'=sp'eed, -150 F. oil-to-bearing temperature,-and F-. water jacket temperature. 'After- -each.test..was'-completed, the ringczone demerit rating-was-determined; :The resultsare shown in the :following -table Ring Lubricant Zone .Demerit Base Oil v -2.1 Base Oil +2% Active Ingredient, Product of Example 1.. 1L1

' The products ofthepresent invention may be employednot only in ordinary hydrocarbon lubricatingoils but also in the'ffheavy duty type of lubricating" oils which have been compounded with such detergent type additives as metal soaps, metal petroleum sulfonates, metalphenates, metal alcoholates, metal alkyl phenol sulfides, metalorgano phosphates, thiophosphates, phosphites and thiophosphites, metal salicyl-ates, metal xanthates and thioxanthates, metal thiocarbamates, aminesand amine derivatives, reaction products of metal phenates andsulfur, reaction products ofmetalphenates and phosphorus sulfides, metal phenolsulfonates and the like. Thus the additives of the present invention maybe used in lubricating oils containing such otheraddition agents as barium tert.-octy1- phenol sulfide, calciumtert-amylphenol sulfide, nickel oleate, barium octadecylate, calcium phenyl stearate, zinc diisopropyl .salicylate, alu minum naphthenate, calcium cetyl phosphate, barium di-tert.-amylphenol sulfide, calcium petroleum sulfonate, zinc methyl cyclohexyl thiophosphate, calcium dichlorostearate, etc. Other types of additives such' as phenols and henol sulfides may be employed.

The lubricating oil base stocks used in the compositions of this invention may be straight mineral lubricatingoils or idistillates derived from paraffinic, naphthenic, asphaltic, or mixed base crudes, or, if desired, various blended oils may be employed as well as residuals, particularly those from which asphaltic constituents have beencarefully removed. The oils maybe refined by conventional methods using acid, alkali and/or clay'or other agentssuch as aluminum chloride, or they may be extracted oils produced; for example, by solvent extraction with solvents of the type ofphenol, sulfur dioxide, furfural, dichlorodiethyl ether, nitrobenzene, crotonaldehyde, etc. Hydrogenated oils, White oils, or shale oilflmay be employed as well as synthetic oils, such as esters and polyethers as well as those prepared, for example, by the polymerization of olefins or by the reaction of oxides of carbon with hydrogen or by the hydrogenation of coal or its products. Also, for special applications, animal, vegetable or fish oils or their hpdrogenated or voltolized products may be employed in admixture with mineral oils.

Fo the best results the base stock chosen should normally be that oil which without the new additive present gives the optimum per iormance in the service contemplated. However, since one advantage of the additives is that their use also makes feasible the employment of less satisfactory mineral oils or other oils, no strict rule can be laid down for the choice of the base stock. Certain essentials must of course be observed. The oil must possess the viscosity and volatility characteristics known to be required for the service contemplated. The oil must be a satisfactory solvent for the additive, although in some cases auxiliary solvent agents may be used. The lubricating oils, however they may have been produced, may vary considerably in viscosity and other properties depending upon the particular use for which they are desired, but they usually range from about 40 to 150 seconds Saybolt viscosity at 210 F. For the lubricating of certain low and medium speed diesel engines the general practice has often been to use a lubricating oil base stock prepared from naphthenic or aromatic crudes and having a Saybolt viscosity at 210 F.

of 45 to90 seconds and a viscosity index of 0 to 50.

10 However, in certain types of diesel engine and, otherg'asoline engine service, oils of higherviscosity index are often preferred, for example, up

to 75 to 100, or even higher, viscosity index.

' In addition to the material to be added according to. the present invention, other agents may also be'usedsuch as dyes, pour depressors, Lhe'at thickened fatty oils, sulfurized fatty oils, organo metallic compounds, metallic or other soaps,

sludge dispersers, anti-oxidants, thickeners, vis

cosity index im'provers, .oiliness agents, resins, rubber,- olefin polymers, voltolized fats, voltolized mineral oils, and/ or voltolized waxes and colloidal solids such'as graphite or zinc oxide, etc. Solvents and assisting agents, such as esters, ketones, alcohols, .aldehydes, halogenated or vnitrated compounds, and the like .may also be employed.

- Assisting agents which are particularly desirable'as plasticizers anddefoamers are the higher alcohols having 8 or more carbon atoms and preferably V12 to-20 carbon atoms. The alcohols may be saturated straight and branched chain aliphatic. alcohols such as octyl alcohol (CsH1'iOH lauryl alcohol (C12H25OH) cetyl alcohol (CisHasOH), stearyl alcohol; sometimes referred to as octadecyl alcohol, (CisHs'zOH), heptadecyl alcohol (C1'1H35OH), and the like; the corresponding olefinic alcohols such as oleyl alcohol;

cyclic alcohols such as naphthenicalcohols; and

aryl substituted alkyl alcohols, for instance,

phenyl octyl alcohol, or octadecyl benzyl alcohol; or mixtures of these various alcohols, which may be pure or substantially pure synthetic alcoholsjv One may also use mixed naturally occurring alcohols such as those found. in wool fat (which is. known to contain a substantial percentage of alcohols having about 16 to 18 carbon atoms) and in sperm oil (which contains a high percentage of cetyl alcohol); and although it is preferable to isolate the alcohols from those materials, for some purposes wool fat, sperm oil or'other natural products rich in. alcohols may; be used per se. Products prepared synthetically by: chemical processes may also be used, such as alcohols pre-" pared by the oxidation of petroleum hydrocar bons, e. g. parafiin Wax, petrolatum, etc.

In addition to being employed in lubricants the additives of the present invention may also be used in motor fuels, hydraulic fluids, torque converter fluids, cutting oils, flushing oils, turbine 011s or transformer oils, industrial oils, process oils and generally as anti-oxidants in mineral oil products. They may also be used in gear lubricants and greases. Since they are powerful surface active agents, they have practical use in dry cleaning fluids; mineral, spirit and aqueous paints, in flotation agents, and as dispersants for insecticides in aqueous and non-aqueous solu tions. They are also valuable anti-oxidants for natural and synthetic rubbers.

What is claimed is:

1. As a new composition of matter a product obtained by reacting one molecular proportion of a phosphorus sulfide with about 1 to about 10 molecular proportions of a hydrocarbon at a temperature of about 290 to about 600 F. and neutralizing the acidic reaction product with an organic basic reacting compound selected from the group consisting of (1) free bases of thecomposition in which R, R, and R" are each members of the group consisting of hydrogen and hydrocarbon 11 radicalscontainingl-20 carbon atoms, and (2) ba'sicreacting salts'of the aforementioned free bases.

2. Acomposition according to claim 1 in'which R,.,R' and R each represent the same atom or group.

3-;Acomposi'tion according to claim 1 in which R; R 'and R" each represent an alkyl group.

4, 'A composition according to claim 1 in which R,'-R' andiR'! each'represent hydrogen.

5. A composition according to claim 1 in which the. phosphorus sulfide-hydrocarbon reaction product is neutralized with guanidine carbonate.

63A composition according to claim 1 in which the acidic reaction product is obtained by reactingphosphorus pentasulfide with a monoolefin.

7. A composition according to claim 6 in which the monoolefin is polyisobutylene.

8.]As'a new composition of matter a product obtained "byjreacting ab'outone molecular proportion of phosphorus pentasulfide with twoto five molecular proportions of polyisobutylene at a temperature of) about 300 to about 550 F., and then'neutralizing'the product thus obtained with guanidine carbonate.

9. A composition accordingto claim 8 in which thefguanidine carbonate is added in the form of a-mixture with water, such mixture containing 30-"70 by weight'of'guanidine carbonate.

10. The processwhic h comprises reacting one molecular proportion of a phosphorus sulfide with about 1 to about 10'molecular proportionszof a hydrocarbon at-a temperature of about 200 to about 600"F. and neutralizing the acidic reaction productwith an organic basic reactingrcompound selectedfro'm the group consisting of: (1) free bases-0f the composition N-R Rz' 7/NR2 inwhich R, R and" R are each members of the group consisting of hydrogen and hydrocarbon radicals containing 1'-20 carbon atoms, and (2) basic reacting salts of the aforementioned free bases; 7

11. A process according to claim 10 in which the phosphorussulfide is phosphorus pentasulfide and in which" the hydrocarbon 'isa monoolefin.

12. A process' according to claim 11 in which the basic reacting compound is guanidine carbonate.

13. A process according'toclaim -11 in which the monoolefin is'polyisobutylene.

14; Aoprocess which comprises reacting about one molecular proportion of phosphorus pentasulfide with two to'five' molecular proportions of polyisobutyleneare temperature of' about 300 to about 550? F., and then'neutralizingthe product'thus obtained with guanidine carbonate.

15. A process accordingto claim 14 inwhich the guanidine carbonate is employed in the form of a mixture'withwater, such mixtur'e'containing 3'0-70% by weight of 'guanidine' carbonate.

16. Asa newcomp'osition of matter a salt of (1) an acidproduct obtained'by reacting one molecular proportion of a phosphorus sulfide'with about one to about ten molecular proportions of a hydrocarbon a't'a temperature' of about 200 to about 600 F; and (2) an organic base of the type VNR R N-( J-N'R in'which R, R- andR" are each members ofthe group consisting of'hydrogen and hydrocarbon radicals containing 1-20' carbon atoms.

REFERENCES CITED The following references are of record'in the file of this patent:

Number -i v Nanie'- Date" 7 2,400,786 Rust -May 215-1946 2,401,733 I-ItlBJ-(i 1 -'June= 11," 1946 24031742: BaltlSofi et a1. July 9; 1946 2,4'49;9 33' Giammaria Sept. 21, 1948 2,449,934 Giammaria" Sept. 21, 1948 2,506,572 Bartleson May 9; 1950 

1. AS A NEW COMPOSITION OF MATTER A PRODUCT OBTAINED BY REACTING ONE MOLECULAR PROPORTION OF A PHOSPHORUS SULFIDE WITH ABOUT 1 TO 10 MOLECULAR PROPORTIONS OF A HYDROCARBON AT A TEMPERATURE OF ABOUT 200* TO ABOUT 600* F. AND NEUTRALIZING THE ACIDIC REACTION PRODUCT WITH AN ORGANIC BASIC REACTING COMPOUND SELECTED FROM THE GROUP CONSISTING OF: (1) FREE BASES OF THE COMPOSITION 